Jian Li,Yaping Lin,Xiulian Pan,Dengyun Miao,Ding Ding,Yi Cui,Jinhu Dong,Xinhe Bao
Strong metal–support interaction (SMSI) has been widely recognized for platinum-group metals on reducible oxide supports. Herein we report that the catalytic activity of Ni catalyst in CO2 methanation is significantly suppressed over conventional anatase (a-TiO2) support due to the SMSI-induced formation of a titania overlayer around the Ni nanoparticles. Furthermore, CO is the only product . In contrast, the NH3-treatment and H2-treatment of the a-TiO2 support enhance remarkably the activity of Ni, i.e., CO2 conversion increases by 1 order of magnitude and CO2 is hydrogenated almost exclusively to CH4. X-ray photoelectron spectroscopy (XPS), H2 and CO chemisorption, and low temperature electron paramagnetic resonance (EPR) reveal that the enhanced CO2 methanation activity may be related with the Ti3+ species in the bulk that are generated by reduction treatment, which likely have altered the SMSI between Ni and a-TiO2 support. This simple reduction treatment approach may be applicable to modulate the SMSI of other reducible oxide-supported metal catalysts.
In-situ C-N-S-tridoped single crystal black TiO 2 nanosheets with exposed {001} facets are successfully fabricated via a facile hydrothermal method combined with an in-situ solid-state chemical reduction approach, followed by calcination at 450 °C. The crystal structure, crystallinity, morphology and composition of the as-prepared samples are investigated through X-ray diffraction, Raman, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV–vis diffuse reflectance spectroscopy, respectively. The results suggest that the obtained C-N-S-tridoped single crystal black TiO 2 nanosheets exhibit uniform nanosheet-like structure with exposed {001} facets and average length of ∼300–400 nm, thickness of ∼20 nm. The visible-light photocatalytic degradation rate of methyl orange is up to 92.13%, and photocatalytic hydrogen evolution is 149.7 μmol h −1 g −1 . The excellent photocatalytic activity can be ascribed to the synergetic effect of surface heterojunction between {001} and {101} facets, the C-N-S-tridoping, and the formed Ti 3+ species in photocatalyst, which can not only favor the visible-light absorption but also facilitate the separation and transfer of photogenerated charges.